Post treatment to reduce shunting devices for physical etching process

ABSTRACT

A method for etching a magnetic tunneling junction (MTJ) structure is described. A stack of MTJ layers is provided on a bottom electrode. A top electrode is provided on the MTJ stack. The top electrode is patterned. Thereafter, the MTJ stack not covered by the patterned top electrode is oxidized or nitridized. Then, the MTJ stack is patterned to form a MTJ device wherein any sidewall re-deposition formed on sidewalls of the MTJ device is non-conductive and wherein some of the dielectric layer remains on horizontal surfaces of the bottom electrode.

PRIORITY DATA

The present application is a continuation application of U.S.application Ser. No. 15/479,514, filed Apr. 5, 2017, which isincorporated herein by reference in its entirety.

TECHNICAL FIELD

This application relates to the general field of magnetic tunnelingjunctions (MTJ) and, more particularly, to etching methods for formingMTJ structures.

BACKGROUND

A typical MTJ etched by a chemical etching process is found to havesidewall damage, possibly caused by oxygen or other chemicals during theetching process. Pure physical etching processes such as ion beametching (IBE) can minimize sidewall damage. However, one drawback of thephysical etching process is the sidewall re-deposition of material fromthe bottom electrode and MTJ materials to the MTJ sidewalls. Thesidewall re-deposition of the bottom electrode will lead to a shuntingpath around the MTJ sidewall and then lead to low yield for the MRAMchip.

Several patents teach methods to reduce shunting. These include U.S.Pat. No. 9,257,638 (Tan et al), U.S. Pat. No. 7,043,823 (Childress etal), U.S. Pat. No. 8,981,507 (Takahashi et al), U.S. Pat. No. 6,798,626(Hayashi et al), U.S. Pat. No. 8,045,299 (Fontana, Jr et al), U.S. Pat.No. 8,673,654 (Hong et al) and U.S. Patent Application 2016/0079308(Ito). U.S. Pat. No. 8,045,299 (Fontana, Jr et al—HGST) teaches etchingand then oxidizing the MTJ stack or adding ozone or water to the etchingprocess to oxidize the re-depositing material.

SUMMARY

It is an object of the present disclosure to provide an improved etchingprocess in forming MTJ structures.

Yet another object of the present disclosure is to provide an etchingprocess that reduces shunting of MTJ devices.

In accordance with the objectives of the present disclosure, a methodfor etching a magnetic tunneling junction (MTJ) structure is achieved. Astack of MTJ layers is provided on a bottom electrode. A top electrodeis provided on the MTJ stack. The top electrode is patterned.Thereafter, the MTJ stack not covered by the patterned top electrode isoxidized or nitridized. Then, the MTJ stack is patterned to form a MTJdevice wherein any sidewall re-deposition formed on sidewalls of the MTJdevice is non-conductive.

BRIEF DESCRIPTION OF THE DRAWINGS

In the accompanying drawings forming a material part of thisdescription, there is shown:

FIGS. 1, 2, 3A, and 4A illustrate in cross-sectional representationsteps in a first preferred embodiment of the present disclosure.

FIGS. 1, 2, 3B, and 4B illustrate in cross-sectional representationsteps in a second preferred embodiment of the present disclosure.

DETAILED DESCRIPTION

For most pure physical etching processes (such as IBE), the sidewallalways suffers a severe re-deposition issue since the by-products of theetched material are non-volatile. To prevent the re-deposition materialaround the MTJ sidewall from becoming a shunting path for the MTJ, weapply a surface treatment by oxygen to convert the potentialre-deposition material from conductive to non-conductive. This step willensure that any re-deposition is non-conductive and will not causeshunting of the MTJ devices.

Referring now particularly to FIGS. 1 through 4, the novel disclosurewill be described in detail. A bottom electrode 12 is formed on thesubstrate 10, as shown in FIG. 1. Now, layers are deposited on thebottom electrode to form a magnetic tunnel junction. Layer 14 includesthe MTJ layers including one or more seed layers, pinned layers, tunnelbarrier layers, and free layers, as is conventional in the art. Finallya top electrode 16 is deposited on the MTJ layers 14.

A photoresist mask 25 is formed over the top electrode. As shown in FIG.2, the top electrode is patterned using the photoresist mask 25.

Now, an additional post treatment process is added in the middle of theetching process. After defining the top electrode 16 and before the mainphysical etching to define the MTJ area, preferably an oxidationtreatment 27 is performed to oxidize the entire exposed MTJ area whereinthe exposed MTJ area not covered by the patterned top electrode becomesoxidized 20 and therefore, non-conductive, as shown in FIG. 3A. That is,the entire stack not covered by the top electrode hard mask is oxidized,including the capping layer, free layer, pinned layer, seed layer and soon. This will ensure that all re-deposition after IBE etching will bestill non-conductive to prevent any shutting path.

Oxidizing the re-deposited material after etching is undesirable becausethe oxygen might damage the MTJ device. It is hard to control thepenetration depth of the oxide. Oxidizing prior to etching does notcause this problem because all of the oxygen will be gone after etching.

After the treatment process, a physical etching will be applied todefine the MTJ area, as shown in FIG. 4A. The additional treatment willnot eliminate sidewall re-deposition, but we can ensure there-deposition material 22 will not be conductive and, thus, it will notlead to a shunting path cross the MTJ barrier. Most of the etchedmaterial should be pumped out during the etching process, but even ifthere is some re-deposition on the MTJ sidewall, it will not become ashutting path because it is not conductive.

Depending on process integration, the bottom electrode could bepatterned prior to depositing the MTJ layers. Or the bottom electrodecould be patterned after patterning the MTJ device. We can eliminate there-deposition shunting problem from the bottom electrode if we increasethe oxidation power and/or time to oxidize the bottom electrode portionnot covered by the top electrode hard mask before we perform the MTJetching, as shown in FIG. 3B. Then, when we pattern the bottomelectrode, any re-deposition 22 on horizontal surfaces of the bottomelectrode layer are removed during this etching. Some re-deposition mayoccur on sidewalls of the MTJ stack, but this will be non-conductivematerial 22, as shown in FIG. 4B.

The post treatment can be applied in a variety of different ways. Thesecan include: 1) Natural oxidation or nitridation by introducing oxygenor nitrogen gas, 2) Oxidation or nitridation with plasma assist orion-beam assist, or 3) Treatment by a liquid such as water or a solvent.It might be necessary to apply the treatment multiple times to ensureall the metallic material in the MTJ stack is converted to oxide ornitride so that it becomes non-conductive.

In option 1, oxygen or nitrogen is introduced into a chamber containingthe wafer prior to MTJ etching. If the MTJ stack is not very thick, thenatural oxidation or nitridation might be enough to convert all of theMTJ stack not covered by the top electrode hard mask to a non-conductivematerial.

In option 2, plasma oxidation or nitridation might use pure O2, pure N2,or a mixture of O2 and N2. The plasma oxidation, nitridation, or mixedO2/N2 can optionally be performed with some noble gas such as Ar, Xe,and the like. O2 or N2 implantation could be performed to transform thematerial. Alternatively, O2 or N2 ion beam irradiation could performoxidation or nitridation of the exposed layer.

In option 3, water or a solvent containing —OH or —NH, for example,could convert the exposed layers to oxides or nitrides.

Since the MTJ layers are oxidized or nitridized before performing themain physical etching, there should be no remaining oxygen or nitrogengas in the area after MTJ etching is completed. This will mitigateoxygen or nitrogen damage to the MTJ sidewalls.

Although the preferred embodiment of the present disclosure has beenillustrated, and that form has been described in detail, it will bereadily understood by those skilled in the art that variousmodifications may be made therein without departing from the spirit ofthe disclosure or from the scope of the appended claims.

What is claimed is:
 1. A method, comprising: forming a patterned topelectrode layer on a stack of material layers, the stack of materiallayers including: a bottom electrode layer; and a magnetic tunnelingjunction (MTJ) stack disposed on the bottom electrode layer, the MTJstack being interposed between the patterned top electrode layer and thebottom electrode layer; converting exposed portions of the MTJ stack toa first non-conductive material, the converting including a firstprocess that utilizes the patterned top electrode layer as a firstprocess mask; and removing the first non-conductive material to form apatterned MTJ stack, the removing including a second process thatutilizes the patterned top electrode layer as a second process mask. 2.The method of claim 1, wherein the first process is selected from thegroup consisting of an oxidation process, a nitridation process, and acombination thereof.
 3. The method of claim 1, wherein the MTJ stackincludes a metal, and wherein the first non-conductive material includesan oxide of the metal, a nitride of the metal, or a combination thereof.4. The method of claim 1, wherein the first process further convertsexposed portions of the bottom electrode layer to a secondnon-conductive material.
 5. The method of claim 4, wherein the removingfurther removes the second non-conductive material, the removing furtherforming a patterned bottom electrode layer.
 6. The method of claim 4,wherein the second non-conductive material includes an oxide of amaterial of the bottom electrode layer, a nitride of the material of thebottom electrode layer, or a combination thereof.
 7. The method of claim1, wherein the second process causes a redepositing of the firstnon-conductive material on sidewalls of the patterned MTJ stack.
 8. Themethod of claim 1, wherein the second process includes a physical etchprocess.
 9. A method, comprising: providing a stack of magnetictunneling junction (MTJ) layers on a bottom electrode layer; forming apatterned top electrode layer on the stack of MTJ layers, wherein afirst portion of the MTJ stack is covered by the patterned top electrodelayer, and wherein second portions of the MTJ stack are exposed by thepatterned top electrode layer; converting, using a nitridizing process,the second portions of the MTJ stack to a non-conductive nitridematerial, the non-conductive nitride material being a nitride of amaterial of the MTJ stack; and removing the non-conductive nitridematerial using the patterned top electrode layer as a mask to therebyform a patterned MTJ stack.
 10. The method of claim 9, wherein thenitridizing process includes exposing the second portions of the MTJstack to a nitrogen-containing fluid.
 11. The method of claim 10,wherein the nitrogen-containing fluid includes nitrogen gas.
 12. Themethod of claim 10, wherein the nitrogen-containing fluid includes aliquid containing an —NH functional group.
 13. The method of claim 9,wherein the nitridizing process includes a plasma nitridation process.14. The method of claim 9, wherein the nitridizing process includes anitrogen ion-beam irradiation process.
 15. The method of claim 9,wherein the removing the non-conductive nitride material includes anion-beam etch process.
 16. A method, comprising: forming a mask layerover a stack of material layers, the stack of material layers including:a substrate; a bottom electrode disposed on the substrate; a magnetictunneling junction (MTJ) stack disposed on the bottom electrode; and atop electrode disposed on the MTJ stack; transferring a pattern of themask layer to the top electrode, the transferring resulting in apatterned top electrode; exposing portions of the MTJ stack exposed bythe patterned top electrode to a first process, the first processconverting the exposed portions of the MTJ stack to a non-conductivematerial; and removing the non-conductive material using a secondprocess that utilizes the patterned top electrode as a process mask, theremoving resulting in a patterned MTJ stack.
 17. The method of claim 16,wherein the removing the non-conductive material using the secondprocess causes a redepositing of the non-conductive material onsidewalls of the patterned MTJ stack.
 18. The method of claim 16,wherein the first process is selected from the group consisting of anoxidation process, a nitridation process, and a combination thereof. 19.The method of claim 16, wherein the non-conductive material includes anoxide of a material of the MTJ stack, a nitride of the material of theMTJ stack, or a combination thereof.
 20. The method of claim 16, whereinthe second process includes a physical etch process.